CN110018621A

CN110018621A - Toner

Info

Publication number: CN110018621A
Application number: CN201811319228.1A
Authority: CN
Inventors: 岛野努; 中川義广; 田川丽央; 下田卓
Original assignee: Canon Inc
Current assignee: Canon Inc
Priority date: 2017-11-07
Filing date: 2018-11-07
Publication date: 2019-07-16
Anticipated expiration: 2038-11-07
Also published as: DE102018127478B4; CN110018621B; DE102018127478A1; JP7005289B2; US20190137901A1; US10437165B2; JP2019086642A

Abstract

A kind of toner is provided, it includes the toner-particle comprising binder resin and wax A, wherein binder resin includes styrene acrylic, the amount of the styrene acrylic in the binder resin is at least 50 mass %, the fusing point of wax A is 60.0 DEG C to 100.0 DEG C, wax A is compatible relative to 100 mass parts Styrene And Butyl-acrylate copolymer at least 15.0 mass parts at 100 DEG C, in the DSC of toner, wherein when carrying out the cooling from 150 DEG C to 0 DEG C with 1.0 DEG C/min, the peak temperature at the exothermic maximum peak from wax A is denoted as Tc (1), Tc (20) are denoted as with the peak temperature at the exothermic maximum peak from wax A when carrying out the cooling from 150 DEG C to 0 DEG C with 20.0 DEG C/min, meet 0.0 DEG C ≤ Tc (1)-Tc (20)≤7.0 DEG C.

Description

Toner

Technical field

It will be by xerography, electrostatic recording or toner injection record method etc. the present invention relates to being used to pass through Latent electrostatic image developing that method is formed and form the toner of toner image.

Background technique

In recent years, the demand further decreased to the power consumption of printer and duplicator is generated.In order to meet the demand, The excellent toner of the toner of Flashmelt at a lower temperature, i.e. low-temperature fixability is preferred.In order to obtain low temperature The excellent toner of fixation performance has been carried out research using wax in toner.

Wax is added with the purpose for plasticity to be assigned to binder resin.Melted due to Yin Re with liquefied wax become with Binder resin is compatible, so viscosity of the toner in melting reduces, and can obtain the excellent toning of low-temperature fixability Agent.

For such background, Japanese patent application discloses No.2017-040772, Japanese patent application discloses No.2017-044952, Japan Patent No.6020458, Japanese patent application disclose No.2012-63574 and Japanese patent application Open No.2006-267516 it has been proposed that using ester type waxes toner.

At the same time, it is also important that printer and duplicator can generate stable image quality for a long time.In order to meet The demand needs mechanical strength and shows the few toner of the ongoing change of image quality when long-term storage.

However, the wax and binder resin that add for plasticity to be assigned to the purpose of binder resin have high-compatibility. Therefore, a part of wax is intended to keep compatible with binder resin in toner production process.As a result, in the presence of wherein mixing colours The case where mechanical strength of agent reduces or the wax compatible with binder resin expose as time go on to the surface of toner Thus the case where reducing image quality.

Therefore, there is demand to the toner for using the wax with high-ductility, which has both low-temperature fixability and machinery The ageing stability of intensity and image quality is excellent.

Summary of the invention

No.2017-040772 is disclosed in Japanese patent application and Japanese patent application discloses public affairs in No.2017-044952 In the toner opened, low-temperature fixability is improved by using ester type waxes, but due to compatible between ester type waxes and binder resin Property is not high enough, so there is still room for further improvement.

Further, No.2012-63574 and Japan Patent Shen are disclosed in Japan Patent No.6020458, Japanese patent application It please disclose in toner disclosed in No.2006-267516, using the ester type waxes with binder resin with high-compatibility, still The investigation for concentrating on ongoing change of the image quality during long-term storage is not disclosed.Accordingly, there exist the ester type waxes of part A possibility that compatible with binder resin is kept during producing toner.Toner is further improved as a result, still having The leeway of the ageing stability of mechanical strength and image quality.

That is, the present invention provides the ageing stability for having both low-temperature fixability and mechanical strength and image quality is excellent Toner.

In the first aspect the present invention provides:

A kind of toner includes the toner-particle comprising binder resin and wax A, wherein

The binder resin includes styrene acrylic,

The amount of the styrene acrylic in the binder resin is at least 50 mass %,

The fusing point of the wax A is 60.0 DEG C to 100.0 DEG C,

The wax A is at 100 DEG C relative to 100 mass parts Styrene And Butyl-acrylate copolymer at least 15.0 mass parts Be it is compatible, the Styrene And Butyl-acrylate copolymer be 75 mass parts styrenic monomers and 25 mass parts acrylic acid fourths The copolymer of ester monomer and with 30,000 weight average molecular weight,

In the differential scanning calorimetry measurement of the toner,

Wherein when carrying out the cooling from 150 DEG C to 0 DEG C with 1.0 DEG C/min the exothermic maximum peak from the wax A peak Value temperature is denoted as Tc (1), and

The peak value at the exothermic maximum peak from the wax A when carrying out the cooling from 150 DEG C to 0 DEG C with 20.0 DEG C/min Temperature is denoted as Tc (20),

The relationship of the Tc (1) and the Tc (20) satisfaction 0.0 DEG C≤Tc (1)-Tc (20)≤7.0 DEG C.

In second aspect the present invention provides:

A kind of toner includes the toner-particle comprising binder resin, wax A and crystalline material, wherein

The binder resin includes styrene acrylic,

The amount of the styrene acrylic in the binder resin is at least 50 mass %,

The wax A is at least 50 mass % relative to the ratio of the wax A and the total amount of the crystalline material,

The fusing point of the wax A is 60.0 DEG C to 100.0 DEG C,

The wax A is the ester of two with 2 to the 6 carbon atoms pure and mild aliphatic monocarboxylic acids with 16 to 22 carbon atoms Compound,

The solubility parameter of the wax A is at least 8.81 (cal/cm³)^1/2,

In the differential scanning calorimetry measurement of the toner,

Wherein the peak temperature at the exothermic maximum peak when carrying out the cooling from 150 DEG C to 0 DEG C with 1.0 DEG C/min is denoted as Tc (1), and

The peak temperature at the exothermic maximum peak when carrying out the cooling from 150 DEG C to 0 DEG C with 20.0 DEG C/min is denoted as Tc (20),

According to the present invention, can provide it is a kind of have both low-temperature fixability and mechanical strength and image quality through Shi Wending The excellent toner of property.

Referring to attached drawing, further characteristic of the invention will become from the description of following exemplary embodiment aobvious and easy See.

Detailed description of the invention

Fig. 1 is the schematic diagram for showing the crystallization process for the wax for having material of low compatibility with adhesive resin.

Fig. 2 is the schematic diagram for showing the crystallization process for the wax for having high-compatibility with binder resin.

Fig. 3 is the schematic diagram for showing the picture pattern for evaluating image quality.

Specific embodiment

In the present invention, unless otherwise defined, indicating that the statement " from AA to BB " of numberical range or " AA to BB " refer to Numberical range including the upper and lower bound as endpoint.

In addition, crystalline material is to observe the compound of endothermic peak in differential scanning calorimetry measurement (DSC).

In order to obtain the excellent toner of ageing stability for having both low-temperature fixability and mechanical strength and image quality, Have to binder resin will there is the wax of high-compatibility to be introduced into the toner under phase-separated state.

In consideration of it, inventors have seen that will be by fully increasing with mutually separating for binder resin The crystallinity of wax and cause, and carried out the extensive research of the idea.Result obtained results in generation of the invention.

Crystallinity refers to the ratio for being added to the wax crystallization of toner.

Specifically, crystallinity is when measuring (hereinafter also referred to as dsc measurement) by the differential scanning calorimetry of carry out toner Caloric receptivity, carry out wax dsc measurement when caloric receptivity and wax input amount calculate.

The present inventor has been carried out in the course of the study using the wax with binder resin with high-compatibility The dsc measurement of toner, and it was found that crystallization temperature is significantly reduced as cooling velocity increases.At the same time, it is using In the toner with binder resin with the wax of material of low compatibility, it was confirmed that crystallization temperature is almost without reduction.

It is based on the research as a result, the present inventor is in view of following.

It is known that, conventionally, be that the crystallization process of wax is made of two processes: crystallization karyogenesis and crystalline growth.

Using the wax with binder resin with material of low compatibility, it is conceivable that partial wax is in melting It is mutually separated with binder resin.When cooling from such state, in the wax direct crystallization of melting phase separation.Therefore, regardless of How is cooling rate, and the nuclei of crystallization promptly generate (Fig. 1) all at substantially constant temperature.

At the same time, when using the wax with binder resin with high-compatibility, it is believed that all wax and binder tree Rouge is compatible in melting.For the crystallization carried out from such state, it is conceivable that the wax compatible with binder resin Assemble first, and the nuclei of crystallization form (Fig. 2) after concentration locally increases.

Therefore, when increasing cooling rate, it is conceivable that the process of wax aggregation becomes the process (rate- of rate decision Determining process), and the rate for generating the nuclei of crystallization reduces, and leads to the reduction of crystallization temperature.

That is, when using the wax with binder resin with high-compatibility, particularly, it is conceivable that crystallization karyogenesis speed Rate reduces, and thinks that, due to this point, the crystallization of wax deficiently carries out, and residual with the component of binder resin compatibilized It stays.

Based on above-mentioned consideration, the inventors found that, using the tune with the wax of binder resin highly compatible In toner, when control nuclei of crystallization generating rate and design toner thus crystallization temperature when increasing cooling rate not When may decline very much, the crystallinity of the wax in toner is significantly improved.

By detailed analysis tune aiming at the problem that present invention is occurred when using the wax with binder resin with high-compatibility Toner and complete, the present invention can not easily be realized based on the prior art.

Toner of the invention are as follows:

Toner with the toner-particle comprising binder resin and wax A, wherein

Binder resin includes styrene acrylic,

The amount of styrene acrylic in binder resin is at least 50 mass %,

The fusing point of wax A is 60.0 DEG C to 100.0 DEG C,

Wax A is phase relative to 100 mass parts Styrene And Butyl-acrylate copolymer at least 15.0 mass parts at 100 DEG C Hold, the Styrene And Butyl-acrylate copolymer is 75 mass parts styrenic monomers and 25 mass parts butyl acrylate lists The copolymer of body and with 30,000 weight average molecular weight,

In the differential scanning calorimetry measurement of toner,

Wherein when carrying out the cooling from 150 DEG C to 0 DEG C with 1.0 DEG C/min the exothermic maximum peak from wax A peak value temperature Degree is denoted as Tc (1), and

The peak temperature at the exothermic maximum peak from wax A when carrying out the cooling from 150 DEG C to 0 DEG C with 20.0 DEG C/min Tc (20) are denoted as,

The relationship of Tc (1) and Tc (20) satisfaction 0.0 DEG C≤Tc (1)-Tc (20)≤7.0 DEG C.

Toner uses the wax A that high-compatibility is shown with the binder resin comprising styrene acrylic.

That is, wax A is relative to 100 mass parts Styrene And Butyl-acrylate copolymer at least 15.0 mass parts at 100 DEG C Compatible.Styrene And Butyl-acrylate copolymer is 75 mass parts styrenic monomers and 25 mass parts Butyl Acrylate Monomers Copolymer and with 30,000 weight average molecular weight.

Compatible amount at 100 DEG C is hereinafter also referred to as saturated compatible amount.

Saturation compatible amount be show numerical value that how many wax A can be compatible with Styrene And Butyl-acrylate copolymer, and In the present invention, it is believed that it is compatible with the binder resin including styrene acrylic that saturation compatible amount shows wax A Property.

When being saturated compatible amount is at least 15.0 mass parts, sufficient low-temperature fixability can be obtained.It is saturated compatible amount The upper limit is 100.0 mass parts, at this point, Styrene And Butyl-acrylate copolymer and wax A are any mixing.

Even if the amount for the wax A for including in the toner-particle be it is identical, the wax with bigger saturation compatible amount more has Improve low-temperature fixability in effect ground.

Saturation compatible amount is preferably at least 25.0 mass parts, more preferably at least 45.0 mass parts.

At the same time, when being saturated compatible amount is less than 15.0 mass parts, as described above, wax A in binder resin Crystallization karyogenesis quickly occurs, so that the ongoing change of toner, that is, the problem to be solved in the present invention, it is less likely hair It is raw, but low-temperature fixability is insufficient.

Saturation compatible amount can be controlled by the solubility parameter (SP value) and molecular weight of wax A.Description is saturated later The measurement method of compatible amount.

SPw and SPc are denoted as respectively in the solubility parameter of wax A and Styrene And Butyl-acrylate copolymer, and wax A Weight average molecular weight is denoted as under the occasion of Mw, and SPw, SPc and Mw preferably satisfy following formula (1), and more preferably meet following formula (1) '.It is molten The unit of solution degree parameter is (cal/cm³)^1/2。

(SPc-SPw)²×Mw≤680 (1)

450≤(SPc-SPw)²×Mw≤650 (1)'

By using the wax A for meeting formula (1), the sufficient compatibility of wax and binder resin can be obtained.Hereinafter will The calculation method of SP value and the measurement method of molecular weight are described.

In the differential scanning calorimetry measurement of toner,

Tc (1)-Tc (20) is hereinafter also referred to as Δ Tc.

Δ Tc is rapid enough no more than 7.0 DEG C of karyogenesis rates meaned in wax A.Therefore, can fully reduce with The amount of the wax A of binder resin compatibilized.As a result, also inhibiting wax even if toner is allowed to be placed under hot and humid environment Expose the surface of toner-particle, and improves the ageing stability of image quality.

In addition, Δ Tc is preferably 0.0 DEG C to 6.5 DEG C, and more preferably 0.0 DEG C to 5.0 DEG C.

Δ Tc can adding by the material of the promotion crystallization karyogenesis in the concentration and wax A of the wax A in control toner Calais's control.The measurement method of Tc (1) and Tc (20) is described below.

The fusing point of wax A is 60.0 DEG C to 100.0 DEG C.

By the way that the fusing point of wax A is set at least 60.0 DEG C, even if when using the wax with big saturation compatible amount, It can inhibit the surface exposure of wax.Further, by setting fusing point to no more than 100.0 DEG C, sufficient low temperature can be obtained Fixation performance.

The fusing point of wax A is preferably 65.0 DEG C to 90.0 DEG C.The fusing point of wax A can be controlled by the constituent material of wax A.Under The measurement method of the fusing point of wax A will be described in text.

The amount of wax A is preferably 1 mass parts to 30 mass parts, relative to 100 mass parts binder resins.

Peak temperature for the exothermic maximum peak in the measurement of the differential scanning calorimetry of toner is the temperature from wax A Degree, wax A are preferably at least 50 mass % relative to the ratio of the total amount of the crystalline material other than wax A and wax A.

When wax A is at least 50 mass % relative to the ratio of the total amount of the crystalline material other than wax A and wax A,

In the differential scanning calorimetry measurement of toner,

The peak temperature Tc (1) at the exothermic maximum peak when carrying out the cooling from 150 DEG C to 0 DEG C with 1.0 DEG C/min, and

The peak temperature Tc (20) at the exothermic maximum peak when carrying out the cooling from 150 DEG C to 0 DEG C with 20.0 DEG C/min is equal From wax A.

Preferably, toner-particle further includes crystalline material, and

In the differential scanning calorimetry measurement of crystalline material,

The peak temperature at the exothermic maximum peak when carrying out the cooling from 150 DEG C to 0 DEG C with 20.0 DEG C/min is denoted as TcB Under the occasion of (DEG C), Tc (20) and TcB meet Tc (20)≤TcB relationship, and more preferably (20)+15.0≤TcB of Tc.

Meeting the condition means that the nuclei of crystallization of crystalline material fully generate before wax A crystallization.As a result, can obtain It must promote the effect of the crystallization karyogenesis in wax A, the Δ Tc of toner can be effectively reduced, and can obtain mechanical strength The excellent toner with ageing stability.In addition, in order to reduce the Δ Tc of toner in the case where not using crystalline material, The amount for increasing wax A is necessary that, so that can be difficult with coexisting for other toner performances in some cases.Hereinafter will The measurement method of TcB is described.

Crystalline material is not particularly limited, and other than known wax, and known crystalline resin also can be used such as Crystalline polyester resin and crystalline propylene's acid system resin.

Moreover it is preferred that crystalline material is copolymerized at 100 DEG C relative to 100 mass parts Styrene And Butyl-acrylates Object with 0.0 mass parts to 5.0 mass parts it is compatible (it is incompatible or be not more than 5.0 mass parts when it is compatible), more preferably with 0.0 matter Measure part to 2.0 mass parts it is compatible (it is incompatible or be not more than 2.0 mass parts when it is compatible).

When compatible amount within the above range when, it is meant that crystalline material and the compatibility of binder resin are sufficiently low.By In low compatibility, it is likely that the nuclei of crystallization of crystalline material are generated, so that the Δ Tc of toner can be reduced more effectively.

The amount of crystalline material is preferably 0.3 mass parts to 6.0 mass parts and more preferably 1.0 mass parts to 3.0 matter Part is measured, relative to 100.0 mass parts binder resins.

Crystalline material is preferably chloroflo B.Promote the effect of the crystallization karyogenesis in wax A also by crystalline material and wax The influence of the compatibility of A.Chloroflo B and the compatibility of wax A are excellent, and the nuclei of crystallization generating rate of chloroflo B itself is high, so that adjusting The Δ Tc of toner can be reduced more effectively.

The example of chloroflo B includes pertroleum wax, chloroflo class and polyolefin-wax.In addition, even if these chloroflos B is used when part of it The substituent groups such as alcohol, amide or carbamate are modified either to be set known to styrene-acrylic etc. Similar effect is also played when those of rouge modification.

Toner differential scanning calorimetry measurement in, it is preferred that when with 10 DEG C/min from when being heated to 150 DEG C for 0 DEG C Endothermic peak caloric receptivity Δ H be 10.0J/g to 35.0J/g.

Caloric receptivity Δ H means the amount for the wax for including in toner.

When the amount is at least 10.0J/g, superior low-temperature fixability can be obtained.

At the same time, when the amount is no more than 35.0J/g, superior mechanical strength can be obtained.

It is further preferred that caloric receptivity Δ H is 20.0J/g to 30.0J/g.The measurement side of caloric receptivity Δ H is described below Method.

It is further preferred that toner-particle further includes non-crystalline polyester resin.

In general, non-crystalline polyester resin has polarity more higher than styrene acrylic system resin, therefore, with nonpolarity The compatibility of wax is low.By the inclusion of non-crystalline polyester resin, the crystallization karyogenesis in wax A can be promoted, so that can obtain The excellent toner of ageing stability.

The amount of non-crystalline polyester resin is preferably 1.0 mass parts to 10.0 mass parts, and more preferably 2.0 mass parts To 8.0 mass parts, relative to 100.0 mass parts binder resins.

As non-crystalline polyester resin, conventionally known polyester resin can be used.

As specific example, non-crystalline polyester resin is by binary acid or derivatives thereof (carboxylic acid halides, ester, acid anhydrides) With dihydric alcohol as polyacid and its derivative (carboxylic acid halides, ester, acid anhydrides), one more than necessary component and optional ternary The dehydrating condensations such as more than first acid, ternary alcohol and monohydric alcohol and obtain.

The example of binary acid includes aliphatic dibasic acid, such as maleic acid, fumaric acid, itaconic acid, oxalic acid, malonic acid, amber Amber acid, dodecyl succinate, dodecenyl-succinic acid, adipic acid, azelaic acid, decanedioic acid and decane -1,10- dicarboxylic acids；Virtue Fragrant race's binary acid, such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalate, monoethyl Dioctyl phthalate, HET acid, himic acid (himic acid), M-phthalic acid, terephthalic acid (TPA) and 2,6- naphthalenedicarboxylic acid.

The example of binary acid derivative include the carboxylic acid halides of aliphatic dibasic acid and aromatic acid, esterification products and Acid anhydrides.

At the same time, the example of dihydric alcohol includes Noncyclic aliphatic glycol, such as ethylene glycol, 1,2-PD, 1,3- Propylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,6-HD, diethylene glycol (DEG), dipropylene glycol, triethylene glycol and neopentyl glycol；Bis-phenol Class, such as bisphenol-A and Bisphenol F；The alkylene oxide adduct of bisphenol-A, such as the ethylene oxide adduct of bisphenol-A and the oxidation third of bisphenol-A Ene adducts；With sub- aralkyl glycol, such as xylyleneglycol.

The example of more than ternary polyacid and its acid anhydrides includes trimellitic acid, and trimellitic anhydride, pyromellitic acid and benzene are equal Four acid anhydrides.

In toner in the dynamic viscoelastic measurement at 100 DEG C, loss elastic modulus G " and Storage elastic modulus G' it 1.50 are preferably not greater than than (G "/G', hereinafter also referred to as tan δ).

In toner, the compatibility of binder resin and wax A are high, and viscosity of the toner in melting becomes extremely low. Therefore, when fixing temperature is high, the hot phenomenon of book contamination that a part of image sticks to fixing member is likely occurred.

When the value of tan δ is no more than 1.50, can obtain superior heat-resisting biofouling.In addition, tan δ is lower, storage Energy elasticity modulus is higher compared to loss elastic modulus.Therefore, it when the value of tan δ is no more than 1.50, can obtain more excellent Mechanical strength.The value of tan δ is more preferably not more than 1.30.At the same time, the lower limit value of tan δ value is not particularly limited, still Preferably about at least 0.70.

Tan δ can be controlled by the amount of the high molecular weight component or cross-linking component for including in toner and the amount of wax A System.The measurement method of tan δ is described below.

The ratio between the weight average particle diameter (D4) and number average bead diameter (D1) of toner (D4/D1) is preferably 1.00 to 1.25.In (D4/ D1) for better image quality can be obtained under occasion no more than 1.25.(D4/D1) 1.20 are more preferably no more than.Toner Weight average particle diameter (D4) and number average bead diameter (D1) can be controlled by the additive amount and fusing point and working condition of wax.Hereinafter The measurement method of the weight average particle diameter (D4) and number average bead diameter (D1) of toner will be described.

Binder resin includes styrene acrylic.

The amount of styrene acrylic in binder resin be at least 50 mass %, preferably 80 mass % extremely 95 mass %.

Styrene acrylic be styrenic monomers and acrylic monomer (acrylic or methacrylic acid and Its Arrcostab) copolymer.

Here, styrene acrylic can include with the state being only made of styrene acrylic In binder resin, or it can be used as and include with or mixtures thereof the block copolymer of other polymers or graft copolymer In binder resin.

When the amount of the styrene acrylic in binder resin is at least 50 mass %, it is saturated compatible amount Value is available.

In addition, can be used for known resin or the polymerization in toner other than styrene acrylic Object can be used for binder resin.

It is, for example, possible to use polyester resin, polyamide, furane resins, epoxy resin, xylene resin and organosilicons Resin.

The example of styrenic monomers presented below.

Styrene, α-methylstyrene, Beta-methyl styrene, o-methyl styrene, m-methyl styrene, to methylbenzene second Alkene, 2,4-DMS and divinylbenzene etc..

Styrenic monomers can be come with independent a kind of or two or more combination in these styrenic monomers It uses.

The example of acrylic monomer presented below.

Alkyl acrylate, such as methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, acrylic acid N-butyl, isobutyl acrylate, tert-butyl acrylate, acrylic acid n-pentyl ester, the just own ester of acrylic acid, 2-EHA, The positive nonyl ester of n-octyl, acrylic acid, the positive last of the ten Heavenly stems ester of acrylic acid and acrylic acid n-dodecane base ester；

Alkyl methacrylate, such as methyl methacrylate, ethyl methacrylate, n propyl methacrylate, first Base isopropyl acrylate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid The positive nonyl of n-pentyl ester, the just own ester of methacrylic acid, 2-Ethylhexyl Methacrylate, n octyl methacrylate, methacrylic acid The positive last of the ten Heavenly stems ester of ester, methacrylic acid and methacrylic acid n-dodecane base ester；

Diester acrylates, such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, poly- second Omega-diol diacrylate and 1,6 hexanediol diacrylate；With

Acrylic acid and methacrylic acid etc..

Acrylic monomer can be come with independent a kind of or two or more combination in these acrylic monomers It uses.

Preferably, styrene acrylic includes selected from by styrene-alkyl acryl ate copolymer and benzene At least one copolymer of the group of ethylene alkyl methacrylate copolymer composition；And

The alkyl of alkyl acrylate and the alkyl of alkyl methacrylate respectively have 2 to 10 carbon atoms, more excellent Select 2 to 8 carbon atoms, even more preferably 2 to 6 carbon atoms.

When the carbon atom number in alkyl within the above range when, can be suitably using the saturation compatible amount based on wax A The toner design of value.Even if when styrene acrylic is not Styrene And Butyl-acrylate copolymer itself, base In the toner design of the value of the saturation compatible amount of wax A be also feasible.

The polymerization ratio (styrenic monomers: acrylic monomer) of styrenic monomers and acrylic monomer is preferably 50:50 to 99:1, more preferably 65:35 are to 80:20.

Wax A is not particularly limited, as long as it is with above-mentioned characteristic, and known wax can be used.

From the viewpoint of the compatibility for the styrene acrylic for including in binder resin, wax A can be with Suitably example is the ester type waxes as alkoxide component and the condensation product of carboxyl acid component.

Specifically, it is preferred that wax A includes the ester compounds of two pure and mild aliphatic monocarboxylic acids.

In addition, wax A is preferably the two pure and mild aliphatic list carboxylics with 16 to 22 carbon atoms with 2 to 6 carbon atoms The ester compounds of acid.

The solubility parameter (SP value) of wax A is preferably at least 8.81 (cal/cm³)^1/2, and more preferably at least 8.83 (cal/cm³)^1/2.The upper limit value of SP value is not particularly limited, it is preferred that being not more than 9.00 (cal/cm³)^1/2。

The example of glycol with 2 to 6 carbon atoms include ethylene glycol, diethylene glycol (DEG), 1,3- propylene glycol, 1,4- butanediol and 1,6-HD.

The example of aliphatic monocarboxylic acid with 16 to 22 carbon atoms includes palmitinic acid, stearic acid He behenic acid etc. Aliphatic monocarboxylic acid.

The amount of wax A is preferably 1 mass parts to 30 mass parts, and more preferably 10 mass parts are to 30 mass parts, relative to 100 mass binder resins.

Toner-particle may include colorant.Colorant can be given as various conventionally known dyestuffs and pigment.

The example of black colorant includes carbon black etc..

The example of yellow colorants includes by Monoazo compound, bis-azo compound, condensation azo-compound, iso-indoles Quinoline ketone compound, isoindoline compounds, benzimidazolone compound, anthraquinone compounds, azo-metal complex, methine Close the yellow uitramarine that object and allyl amide compound represent.

Specific example includes C.I. pigment yellow 74,93,95,109,111,128,155,174,180 and 185.

The example of magenta coloring agent includes Monoazo compound, condensation azo-compound, diketopyrrolo-pyrrole chemical combination Object, anthraquinone compounds, quinacridone compound, basic dye lake compound, naphthol compound, benzimidazolone compound, Thioindigo compound and compound.

Specific example include C.I. paratonere 2,3,5,6,7,23,48:2,48:3,48:4,57:1,81:1,122,144, 146,150,166,169,177,184,185,202,206,220,221,238,254,269 and C.I. pigment violet 19.

The example of cyan colorant includes by copper phthalocyanine compound and its derivative, anthraquinone compounds and basic dye lake The green pigment that compound represents.

Specific example includes C.I. pigment blue 1,7,15,15:1,15:2,15:3,15:4,60,62 and 66.

The conventionally known various dyestuffs for colorant can be used together with pigment.

The amount of colorant is preferably 1.0 mass parts to 20.0 mass parts, relative to 100 mass parts binder resins.

If it is necessary, toner-particle may include known material, such as charge control agent, charge control resin and pigment Dispersing agent.

Toner can also be by optionally mixing toner-particle and external additive and adhering to external additive It is obtained to its surface.

The example of external additive include selected from silica fine particles, aluminum oxide fine particles and titanium oxide fine particle or The fine inorganic particles of its composite oxides.

The example of composite oxides includes silica-alumina fine grained and strontium titanates fine grained.

The additive amount of external additive is preferably 0.01 mass parts to 8.0 mass parts, more preferably 0.1 mass parts to 4.0 Mass parts, relative to 100 mass parts toner-particles.

Toner-particle can be by known to comminuting method, suspension polymerization, emulsion aggregation, dissolution suspension method etc. Production method produces, and its production method is not particularly limited.

The production method of toner is not particularly limited, and may include following steps in the production process of toner-particle (i) and any one of (ii).

(i) it is formed including wax A in water-medium and is capable of forming the binder comprising styrene acrylic The particle of the polymerizable monomer composition of the polymerizable monomer of resin, and make include in the particle of polymerizable monomer composition The step of polymerizable monomer polymerize (suspension polymerization).

(ii) it is formed in water-medium by the way that wax A and binder resin comprising styrene acrylic is molten The particle of the resin solution obtained in organic solvent is solved or be scattered in, and removes include in the particle of resin solution organic molten The step of agent (dissolution suspension method).

Hereinafter, the measurement method of the physical property of toner and constituent material will be described.

Wax measures in the following manner relative to the saturation compatible amount of Styrene And Butyl-acrylate copolymer at 100 DEG C.

Styrene And Butyl-acrylate copolymer is 75 mass parts styrenic monomers and 25 mass parts Butyl Acrylate Monomers Copolymer and with 30,000 weight average molecular weight.

1.00g Styrene And Butyl-acrylate copolymer will be amounted to weigh in 30mL bottle and be heated to 100 DEG C.It Afterwards, it adds wax in bottle, be thoroughly mixed at 100 DEG C and visually observe.

In the case where observation discovery mixture by visual observation is transparent occasion, determine that compatibility is feasible.

The wax for adding 0.005g (being 0.5 mass parts relative to Styrene And Butyl-acrylate copolymer), to obtain determination Maximum when compatibility.

Solubility parameter (SP value) is obtained using Fedors equation (2).

For the value of given below Δ ei and Δ vi, referring to " atom recorded in coating base science and atomic group Evaporation energy and molal volume (25 DEG C), the 54-57 pages, 1986 (Maki Shoten) table 3-9 ".

The unit of SP value is (cal/cm³)^1/2, but because 1 (cal/cm³)^1/2=2.046 × 10³(J/m³)^1/2, it can To be scaled (J/m³)^1/2。

δ i=(Ev/V)^1/2=(Δ ei/ Δ vi)^1/2 (2)

Ev: evaporation energy

V: molal volume

Δ ei: component i atom or the evaporation energy of atomic group

Δ vi: the atom of component i or the molal volume of atomic group

The weight average molecular weight (Mw) of wax is measured in the following manner by gel permeation chromatography (GPC).

Firstly, at room temperature, wax is dissolved in tetrahydrofuran (THF).In the case where wax is difficult to the occasion dissolved, by wax not It is heated in the range of greater than 35 DEG C.Then, the solvent resistance molecular filter " Mysyori that resulting solution is 0.2 μm by aperture Disk " (being manufactured by Tosoh Corporation) filtering, to obtain sample solution.Sample solution is adjusted so that dissolving in THF In component concentration be 0.8 mass %.The sample solution is used to carry out the measurement under the following conditions.

Equipment: high speed GPC equipment " HLC-8220GPC " [is manufactured] by Tosoh Corporation

Column: 2 groups of LF-604 [being manufactured by Showa Denko KK]

Eluent: THF

Flow velocity: 0.6mL/ minutes

Oven temperature: 40 DEG C

Sample injection rate: 0.020mL

In order to calculate the molecular weight of sample, utilization standard polystyrene resin (trade name " TSK Standard is used Polystyrene F-850、F-450、F-288、F-128、F-80、F-40、F-20、F-10、F-4、F-2、F-1、A-5000、A- 2500, A-1000, A-500 " are manufactured by Tosoh Corporation) preparation molecular weight calibration curve.

The Tc (1) and Tc (20) of toner use differential scanning calorimeter " Q1000 " (being manufactured by TA Instruments) To measure.

The fusing point of indium and zinc is used for the temperature correction of equipment detection unit, and the fusing heat of indium is for correcting calorie value.

Specifically, 3mg toner accurate weighing is gone out and is put into aluminium dish.Use empty aluminium dish as reference, and It is maintained 5 minutes with 10 DEG C/min of heating rate from 0 DEG C of raising temperature to 150 DEG C and at 150 DEG C.

Later, the cooling carried out from 150 DEG C to 0 DEG C with 1.0 DEG C/min of cooling rate.Source in DSC curve at this time Tc (1) is taken as from the peak temperature at the exothermic maximum peak of wax A.

At the same time, when the cooling rate for being cooled to 0 DEG C from 150 DEG C changes into 20.0 DEG C/min in DSC curve The peak temperature at the exothermic maximum peak from wax A is taken as Tc (20).

The fusing point and crystallization temperature (TcB) of wax and crystalline material are using differential scanning calorimeter " Q1000 " (by TA Instruments manufacture) it measures.

Specifically, 1mg wax or crystalline material accurate weighing are gone out and is put into aluminium dish.Use empty aluminium dish as ginseng According to, and maintained 5 minutes with 10 DEG C/min of heating rate from 0 DEG C of raising temperature to 150 DEG C and at 150 DEG C.

Later, the cooling carried out from 150 DEG C to 0 DEG C with 20.0 DEG C/min of cooling rate.At this time in DSC curve The peak temperature at exothermic maximum peak is taken as the crystallization temperature of wax or crystalline material.

Then, after being maintained 5 minutes at 0 DEG C, with 10 DEG C/min of heating rate from 0 DEG C of raising temperature to 150 DEG C. The peak temperature at the exothermic maximum peak in DSC curve is taken as the fusing point of wax or crystalline material at this time.The knot of crystalline material Brilliant temperature is TcB.

The caloric receptivity Δ H of toner is surveyed using differential scanning calorimeter " Q1000 " (being manufactured by TA Instruments) Amount.

Specifically, 3mg toner accurate weighing is gone out and is put into aluminium dish.Use empty aluminium dish as reference, and With 10 DEG C/min of heating rate from 0 DEG C of raising temperature to 150 DEG C.The caloric receptivity of the endothermic peak in DSC curve is taken as at this time The caloric receptivity Δ H of toner.When observing multiple endothermic peaks (for example, observing wax A and crystalline material in DSC curve Endothermic peak) when, the caloric receptivity obtained and adding up to the caloric receptivity of each endothermic peak is taken as the caloric receptivity Δ H of toner.

As measuring device, (manufactured by TA Instruments) using rotary plate rheometer " ARES ".

It is 7.9mm and the discoid sample with a thickness of 2.0 ± 0.3mm that diameter will be pressed by using tabletting forming machine As the measurement sample under 25 DEG C of environment.

Sample is mounted on the parallel-plate that diameter is 8.0mm, temperature was increased to from (25 DEG C) of room temperature by 15 minutes 100 DEG C, the shape of sample is adjusted, and after being kept for 10 minutes, starts to measure.

100 DEG C of temperature, the frequency of 1.0Hz and 1.0% strain under conditions of measure.

The loss elastic modulus G obtained by measurement " is tan δ with the ratio between Storage elastic modulus G' (G "/G').

The size distribution of toner calculates as follows.

Accurate particle size distribution measurement equipment " Coulter Counter that is based on hole electric-resistivity method and being equipped with 100 μm of mouth pipes Multisizer 3 " (registered trademark is manufactured by Beckman Coulter, Inc.) is used as measuring device.

The attached special-purpose software of equipment " Beckman Coulter Multisizer 3Version 3.51 " (by Beckman Coulter, Inc. manufacture) for setting measuring condition and analyzing measurement data.With 25,000 channels (channels) effective Measurement channel number measures.

By the way that superfine sodium chloride is dissolved in the solution prepared in ion exchange water to the concentration of about 1 mass %, for example, " ISOTON II " (is manufactured) by Beckman Coulter, Inc., may be used as the electrolytic aqueous solution for being ready to use in measurement.

Special-purpose software is set in the following manner before measurement and analysis.

In " the CHANGE STANDARD OBSERVATION METHOD (change standard operating instructions) of special-purpose software (SOM) " in interface, the tale of control model is set as 50,000 particle；Pendulous frequency is set as 1 time；And " mark will be used 10.0 μm of quasi- particle " (being manufactured by Beckman Coulter, Inc.) resulting value is set as Kd value.Pass through pressing " MEASUREMENT BUTTON OF THE THRESHOLD/NOISE LEVEL (threshold value/noise level measures button) " is automatic Ground given threshold and noise level.In addition, electric current is set as 1,600 μ A；Gain (gain) is set as 2；Electrolyte is set as ISOTON II；Final election " FLUSH OF APERTURE TUBE AFTER MEASUREMENT (rinse mouth pipe after measurement) ".

In " the PULSE TO PARTICLE DIAMETER CONVERSION SETTING (pulse to partial size of special-purpose software Conversion setting) " in interface, element spacing (bin interval) is set as logarithm partial size；By partial size element (particle Diameter bin) it is set as 256 partial size elements；And particle size range is set as 2 μm to 60 μm.

Specific measurement method is described below.

(1) 200mL electrolytic aqueous solution is put into the dedicated 250mL glass round bottom beaker of Multisizer 3, by the burning Cup is placed on sample stage, and is stirred counterclockwise with stirring rod with 24 revolutions per seconds.Pass through " the FLUSH OF of special-purpose software APERTURE (flushing of mouth pipe) " function removes the dirt and bubble in mouth pipe.

(2) 30mL electrolytic aqueous solution is put into 100mL flat bottom glass beaker.Then, addition is by with ion exchange water 3 Quality dilute again " CONTAMINON N " (pH 7 fine measuring instrument cleaning use mild detergent 10 mass % aqueous solutions, It is made of nonionic surfactant, anionic surfactant and organic washing-assisting detergent；By Wako Pure Chemical Industries, Ltd. manufacture) obtain 0.3mL dilution.

(3) preparing to have 120W electricity output and be equipped with frequency of oscillation is 50kHz and two of 180 ° of phase offset oscillations Device ultrasonic dispersing machine " Ultrasonic Dispersion System Tetora 150 " (by Nikkaki Bios Co., Ltd. it manufactures).3.3L ion exchange water will be amounted to be put into the sink of the ultrasonic dispersing machine, and by 2mL's CONTAMINON N is added in sink.

(4) beaker in above-mentioned (2) is placed in the beaker fixation hole of above-mentioned ultrasonic dispersing machine, opens ultrasonic wavelength-division Dissipate machine.Then, the height and position of beaker is adjusted in a manner of keeping the resonance state of the liquid level of the electrolytic aqueous solution in beaker maximum.

(5) in the state of electrolytic aqueous solution in the beaker in (4) above-mentioned with ultrasonic irradiation, by toner with primary It is added to aliquot in above-mentioned electrolytic aqueous solution and is dispersed therein to obtain 10mg toner.Then, it continues to surpass Sound wave decentralized processing 60 seconds.In ultrasonic wave dispersion, the temperature that the water temperature in sink is 10 DEG C to 40 DEG C is suitably adjusted.

(6) pipette is used, the electrolytic aqueous solution for being dispersed with toner in above-mentioned (5) is instilled in above-mentioned (1) The concentration for being placed in the round bottom beaker on sample stage, and having adjusted measurement is 5%.Then, it measures until measurement The quantity of grain reaches 50,000.

(7) measurement data then is analyzed with the special-purpose software provided by device, and it is equal to calculate weight average particle diameter (D4) sum number Partial size (D1).

Embodiment

Thereafter, the present invention will be described in detail referring to embodiment, but the present invention is not only restricted to these embodiments.Embodiment In, unless otherwise specified, part and percentage are on the basis of quality.

The propylene oxide 2mol adduct and 0.35mol second two of 1.0mol terephthalic acid (TPA), 0.65mol bisphenol-A will be amounted to Alcohol is added in the reaction vessel equipped with blender, thermometer, nitrogen ingress pipe, dehydrating tube and decompressor, is then being stirred It mixes down and is heated to 130 DEG C of temperature.

Later, it is added in 100.0 parts of total amount of monomer using 0.52 part of two (2 ethyl hexanoic acid) tin as esterification catalyst, Then temperature is increased to 200 DEG C, and carries out polycondensation until obtaining desired molecular weight.

In addition, addition 0.03mol trimellitic anhydride, to obtain non-crystalline polyester resin 1.

The weight average molecular weight (Mw) of thus obtained non-crystalline polyester resin 1 is 6000, glass transition temperature (Tg) It is 49 DEG C, acid value is 11.2mg KOH/g.

To amount to 1.0mol decanedioic acid and 1.0mol 1,12- dodecanediol be added to equipped with blender, thermometer, In the reaction vessel of nitrogen ingress pipe, dehydrating tube and decompressor, it is then heated to 130 DEG C of temperature under stiring.

Later, 0.7 part of isopropyl titanate (IV) is added in 100.0 parts of total amount of above-mentioned monomer as esterification catalyst, Temperature is increased to 180 DEG C, and carries out reaction until reaching desired molecular weight, thus to obtain crystallinity while decompression Polyester resin (crystalline material B4).

The weight average molecular weight (Mw) of gained crystalline material B4 is 20,000, and fusing point (Tm) is 82.1 DEG C, crystallization temperature It (TcB) is 68.0 DEG C.

Table 1 and 2 shows title and physical property for the wax A in embodiment and comparative example and crystalline material.

[table 1]

In table,

SPw and SPc indicates the solubility parameter (SP value) of wax A and Styrene And Butyl-acrylate copolymer, and Mw is indicated The weight average molecular weight of wax A.

Unit (the cal/cm of solubility parameter (SP value)³)^1/2。

[table 2]

The Production Example of toner is illustrated below.Toner 1 to 17 is produced as embodiment, and toner 18 to 26, which is used as, to be compared Example production.

60.0 parts of styrene

6.0 parts of colorant

(C.I. pigment blue 15: 3, manufactured by Dainichiseika Color&Chemicals Mfg.Co., Ltd.)

Above-mentioned material is put into grater (being manufactured by Mitsui Miike Machinery Co., Ltd.), and is made The zirconium oxide bead for being 1.7mm with diameter further disperses 5 hours at 220rpm, to obtain dispersible pigment dispersion.

Above-mentioned material is mixed and is added to dispersible pigment dispersion.Gained mixture is maintained at 60 DEG C, and is polymerize Property monomer composition by by means of use T.K.Homomixer (mixer for well-distribution) (by Tokushu Kika Kogyo Co., Ltd. manufacture) it stirs at 500 rpm and equably dissolves and disperse to prepare.

At the same time, by the Na of 850.0 parts of 0.10mol/L₃PO₄Aqueous solution and 8.0 part 10% of hydrochloric acid are added to and are equipped with In the container of high-speed mixer CLEARMIX (being manufactured by M Technique Co., Ltd.), rotation speed is adjusted to 15, 000rpm, and carry out being heated to 70 DEG C.

Then, the CaCl of 68.0 parts of 1.0mol/L is added₂Aqueous solution is situated between with preparing the water system comprising calcium phosphate compound Matter.

After polymerizable monomer composition is put into water-medium, 9.0 parts of tert-Butyl peroxypivalate conducts are added Polymerization initiator, and carry out being granulated 10 minutes while maintaining the rotation speed of 15,000rpm.Later, by blender from High-speed mixer is changed to propeller agitation blade, carries out reaction 5 hours at 70 DEG C while reflux, then sets liquid temperature Determine to 85 DEG C, and reacts further progress 2 hours.

It is after polymerization reaction is completed, resulting slurry is cooling, part of it is taken out, and measure size distribution.

In addition, hydrochloric acid is added in slurry to adjust pH as 1.4, and synthos are dissolved by stirring 1 hour. Later, it by the water washing of slurry triplication, filters, it is dry, it is then classified, to obtain toner-particle.

Later, 100.0 parts of toner-particles are used as dimethicone (the 20 mass %) processing of external additive, addition 2.0 parts be charged by friction to polarity (negative polarity) identical with toner-particle and experienced hydrophobic treatment silica it is thin Particle (the number average bead diameter of primary particle: 10nm, BET specific surface area: 170m²/ g), and use Mitsui Henschel mixer (being manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) carries out mixing 15 minutes at 3,000 rpm, To obtain toner 1.

Type and additive amount, the type of crystalline material and additive amount and polymerization in addition to changing wax A as shown in table 3 Other than the type and additive amount of property monomer, toner 2 to 16 and 18 to 25 is obtained in a manner of identical with the Production Example of toner 1 ?.

However, adding 1.0 parts of salumin compound (Bontron E-88, by Orient in the production of toner 12 Chemical Industries, Ltd. manufacture), without adding non-crystalline polyester resin 1.

[table 3]

In table, n-BA indicates that n-butyl acrylate, EA indicate that ethyl acrylate, OA indicate that 2-ethyl hexyl acrylate, DVB indicate two Vinyl benzene.

(preparation of masterbatch)

40 parts of C.I. pigment blue 15s will be amounted to: 3 (by Dainichiseika Color&Chemicals Mfg.Co., Ltd. Manufacture), 60 parts of Styrene And Butyl-acrylate copolymer (styrene: butyl acrylate (mass ratio)=75:25, glass transition Temperature (Tg)=52 DEG C, weight average molecular weight (Mw)=70,000, number-average molecular weight (Mn)=12,000, peak molecular weight (Mp)= 35,000) it is mixed in a in a henschel mixer with 30 parts of water, to obtain the mixture that water is impregnated in pigment aggregation body.It will mix It closes object and the kneading of the twin-roll mill at 130 DEG C 60 minutes is set in by the surface temperature of roller, then crush, to obtain masterbatch.

(preparation of pigment/wax dispersion)

To amount to 970 parts of Styrene And Butyl-acrylate copolymers, 190.5 parts of wax A1,38.1 parts of crystalline material B1 and 1450 parts of ethyl acetate/methyl ethyl ketone mixed liquor (60/40 [volume %]) investment is equipped in the container of stirring rod and thermometer, It stirs lower temperature and is increased to 80 DEG C, and temperature is kept for 5 hours at 80 DEG C.

Then, 500 parts of masterbatch and 330 parts of ethyl acetate/methyl ethyl ketone mixed liquor (60/40 [volume %]) are put into the container In and mix 1 hour, to obtain material solution.

1500 parts of material solution investment graters (being manufactured by Mitsui Miike Machinery Co., Ltd.) will be amounted to In and by using diameter be 1.7mm zirconia particles further disperse at 220rpm 5 hours, thus obtain pigment/ Wax dispersion.

Mixture is adjusted by addition ethyl acetate/methyl ethyl ketone mixed liquor (60/40 [volume %]), so that pigment/wax The solid component concentration of dispersion liquid is 50%.In addition, material solution is heated to 60 DEG C.

(preparation of water phase)

The Na of 850.0 parts of 0.10mol/L will be amounted to₃PO₄Aqueous solution and 8.0 part 10% of hydrochloric acid are added to equipped with high speed In the container of blender CLEARMIX (being manufactured by M Technique Co., Ltd.), rotation speed is adjusted to 15,000rpm, and And it carries out being heated to 60 DEG C.Then, the CaCl of 68.0 parts of 1.0mol/L is added₂Aqueous solution, so that preparation includes calcium phosphate chemical combination The water phase of object.

(granulation/solvent removes)

It will amount in 200.0 parts of pigment/wax dispersion investment water phase, and in temperature and the high-speed mixer for maintaining 60 DEG C It directly carries out being granulated 10 minutes while the rotation speed of middle 15,000rpm.Later, blender is changed to from high-speed mixer Blender equipped with propeller agitation blade, and carry out solvent at 80 DEG C and remove 5 hours, to obtain slurry.

(washing/drying/outside addition)

It is after solvent removes completion, resulting slurry is cooling, part of it is taken out, and measure size distribution.

Later, 100.0 parts of toner-particles are used as dimethicone (the 20 mass %) processing of external additive, addition 2.0 parts be charged by friction to polarity (negative polarity) identical with toner-particle and experienced hydrophobic treatment silica it is thin Particle (the number average bead diameter of primary particle: 10nm, BET specific surface area: 170m²/ g), and it is mixed by using MITSUI Henschel Conjunction machine (being manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) carries out 15 points of mixing at 3,000 rpm Clock, to obtain toner 17.

Other than not adding crystalline material B1 in the Production Example in toner 17, with in the Production Example of toner 17 Identical mode obtains toner 26.

About resulting toner 1 to 26, make to measure physical property with the aforedescribed process.As a result it is summarized in table 4.

[table 4]

Performance evaluation is carried out to resulting toner 1 to 26 according to following methods.As a result it is shown in Table 5.

[low-temperature fixability]

Low-temperature fixability by evaluate visible image deflects do not occur in fixing image when minimum fixing temperature come Evaluation.

Note: the visible image deflects generated during low-temperature fixing are mainly since the toner not melted occurs It is cold to be stained (cold offset).

It is evaluated in the following manner.

Prepare color laser printer (the HP Color Laser Jet 3525dn, by HP for therefrom removing fixation unit Corporation manufacture), toner is taken out from cyan box, and instead fill toner to be evaluated.

Next, in image-receiving sheet, (office planner is manufactured by Canon Inc.；64g/m²) on, by making With the toner of filling, form 2.0cm's long and 15.0cm wide on part of the direction apart from upper end 1.0cm passing through along paper Unfixed toner image (toner bearing capacity: 0.9mg/cm²)。

Next, the fixation unit of transformation removal is adjustable so as to fixing temperature and processing speed, and changed using this The fixation unit made carries out the Fixing Test of unfixed image.

Firstly, processing speed is set as 300mm/s, initial temperature setting under ambient temperature and moisture environment (23 DEG C, 60%RH) It is 150 DEG C, set temperature increases by 5 DEG C every time in proper order, and unfixed image is fixed at each temperature.About resulting fixing Image, low-temperature fixability by using the cold fixing temperature being stained when not occurring as minimum fixing temperature, according to following standard come Evaluation.

A: minimum fixing temperature is no more than 155 DEG C

B: minimum fixing temperature is 160 DEG C

C: minimum fixing temperature is 165 DEG C

D: minimum fixing temperature is 170 DEG C

E: minimum fixing temperature is at least 175 DEG C

[heat-resisting biofouling]

It is heat-resisting biofouling to be evaluated according to following standard in low-temperature fixing test.Do not occur using by being stained from heat Maximum temperature in subtract minimum fixing temperature and the value (hereinafter also referred to as W) that obtains, and carried out according to following standard It determines.

A:W is at least 55 DEG C

B:W is 45 DEG C or 50 DEG C

C:W is 35 DEG C or 40 DEG C

D:W is 25 DEG C or 30 DEG C

E:W is no more than 20 DEG C

[image quality (being averaged for the mechanical strength of toner)]

By in order to commercially available color laser printing is transformed and can also operate when installing only one color processing box Machine (HP Color Laser Jet 3525dn, manufactured by HP Corporation) is evaluated.Removal is installed on the colour The toner for including in cyan box in laser printer, the inside of the box is cleaned by drying, and instead Fill toner to be evaluated (200g).

The figure that printing rate is 1% is by using the OFFICE PLANNER (64g/m manufactured by Canon Inc.²) as figure It is continuously printed upon on 1000 paper under ambient temperature and moisture environment (23 DEG C, 60%RH) as receiving paper.

After printing, an image with white background portions is by using the OFFICE manufactured by Canon Inc. PLANNER(64g/m²) image-receiving sheet is used as to export.Later, the concentration that hazes (%) (=Dr (%)-Ds (%)) is by having The whiteness (reflectivity Ds (%)) and image-receiving sheet of the white background portions of the image of white background portions are relative to white Difference between the whiteness (average reflectance Dr (%)) of the image of color background parts calculates.Whiteness " REFLECTMETER MODEL TC-6DS " (is manufactured) measurement by Tokyo Denshoku Co., Ltd..Amber colo(u)r filter is used as optical filter.

The concentration that hazes is higher, and the mechanical strength of toner is lower, it means that for example defeated due to 1000 print papers The deterioration of the toners such as the exposing of the wax promoted out.

The concentration that hazes is evaluated according to following standard.

A: the concentration that hazes is less than 0.3%

B: the concentration that hazes is at least 0.3% and less than 0.8%

C: the concentration that hazes is at least 0.8% and less than 1.3%

D: the concentration that hazes is at least 1.3% and less than 2.0%

E: the concentration that hazes is at least 2.0%

[ageing stability of image quality]

Prepare by with image quality evaluate in it is identical in a manner of the color laser printer be transformed and with toning to be evaluated The box of agent filling.

The figure that printing rate is 1% is by using the OFFICE PLANNER (64g/m manufactured by Canon Inc.²) as figure It is continuously printed upon on 50 paper under ambient temperature and moisture environment (23 DEG C, 60%RH) as receiving paper.

After printing, such as shown in Fig. 3, have after the white space of 30mm in the top of transfer materials 10 paper of the band-like image of 150mm wide and 30mm long are by using the OFFICE PLANNER manufactured by Canon Inc. (64g/m²) image-receiving sheet is used as to export.

Measure the image color of band-like image.Measurement for image color uses " MACBETH REFLECTION DENSITOMETER RD918 " (is manufactured) by Macbeth Co..Measurement is relative to the white background portions with 0.00 concentration The relative concentration for exporting image, to each output image in the left-hand component of band-like image, center portion and right-hand component It is measured at three points, and image color exports the average value of image by 10 to evaluate.

Later, the box filled with toner to be evaluated is placed 20 days under hot and humid environment (40 DEG C, 95%RH). Hereafter, humidity regulation is further progress 1 day under ambient temperature and moisture environment (23 DEG C, 60%RH), and the figure that printing rate is 1% is logical It crosses using the OFFICE PLANNER (64g/m manufactured by Canon Inc.²) be used as image-receiving sheet in ambient temperature and moisture environment (23 DEG C, 60%RH) under be continuously printed upon on 1000 paper.

Thereafter, which is measured in a manner of identical in the measurement with above-mentioned image color.

In the case where allowing to be placed in hot and humid environment, the big toner of the difference of the image color of front and back means such as wax The deteriorations such as exposing occur on the surface of toner, and the ageing stability of image quality is bad.Image quality Ageing stability is evaluated according to following standard.

A: the reduced rate of image color is less than 2%

B: the reduced rate of image color is at least 2% and less than 5%

C: the reduced rate of image color is at least 5% and less than 10%

D: the reduced rate of image color is at least 10% and less than 20%

E: the reduced rate of image color is at least 20%

[production stability]

The size distribution of suspension in toner production process after reaction step or after solvent removal stage The ratio between middle weight average particle diameter (D4) and number average bead diameter D1 (μm) (D4/D1) are evaluated according to following standard.

A:D4/D1 is less than 1.20

B:D4/D1 is at least 1.20 and less than 1.25

C:D4/D1 is at least 1.25 and less than 1.30

D:D4/D1 is at least 1.30 and less than 1.35

E:D4/D1 is at least 1.35

[table 5]

Although the embodiment of reference example describes the present invention, it will be understood that the present invention be not limited to it is disclosed Illustrative embodiment.Scope of the appended claims should meet broadest explanation, with cover all such modifications and Equivalent structure and function.

Claims

1. a kind of toner comprising: the toner-particle comprising binder resin and wax A, it is characterised in that:

The binder resin includes styrene acrylic,

The amount of the styrene acrylic in the binder resin is at least 50 mass %,

The fusing point of the wax A is 60.0 DEG C to 100.0 DEG C,

The wax A is phase relative to 100 mass parts Styrene And Butyl-acrylate copolymer at least 15.0 mass parts at 100 DEG C Hold, the Styrene And Butyl-acrylate copolymer is 75 mass parts styrenic monomers and 25 mass parts butyl acrylate lists The copolymer of body and with 30,000 weight average molecular weight,

In the differential scanning calorimetry measurement of the toner,

Wherein when carrying out the cooling from 150 DEG C to 0 DEG C with 1.0 DEG C/min the exothermic maximum peak from the wax A peak value temperature Degree is denoted as Tc (1), and

The peak temperature at the exothermic maximum peak from the wax A when carrying out the cooling from 150 DEG C to 0 DEG C with 20.0 DEG C/min Tc (20) are denoted as,

2. toner according to claim 1, wherein

The toner-particle also includes crystalline material,

In the differential scanning calorimetry measurement of the crystalline material,

Wherein the peak temperature at the exothermic maximum peak when carrying out the cooling from 150 DEG C to 0 DEG C with 20.0 DEG C/min is denoted as TcB, The unit of the TcB be DEG C,

The Tc (20) and the TcB meet Tc (20)≤TcB relationship.

3. toner according to claim 2, wherein the crystalline material is at 100 DEG C relative to 100 mass parts institutes It is compatible to 5.0 mass parts with 0.0 mass parts to state Styrene And Butyl-acrylate copolymer.

4. toner according to claim 2 or 3, wherein the crystalline material includes chloroflo B.

5. toner according to claim 1 or 2, wherein

In the differential scanning calorimetry measurement of the toner,

The caloric receptivity Δ H of endothermic peak when being heated to 150 DEG C from 0 DEG C with 10 DEG C/min is 10.0J/g to 35.0J/g.

6. toner according to claim 1 or 2, wherein the toner-particle also includes non-crystalline polyester resin.

7. toner according to claim 1 or 2, wherein loss elastic modulus G " of the toner at 100 DEG C with The ratio between Storage elastic modulus G' is no more than 1.50.

8. toner according to claim 1 or 2, wherein

The styrene acrylic includes selected from by styrene-alkyl acryl ate copolymer and styrene-methyl At least one copolymer of the group of alkyl acrylate copolymer composition, and

The alkyl of the alkyl of the alkyl acrylate and the alkyl methacrylate respectively has 2 to 10 carbon atoms.

9. a kind of toner comprising: the toner-particle comprising binder resin, wax A and crystalline material, feature exist In:

The binder resin includes styrene acrylic,

The amount of the styrene acrylic in the binder resin is at least 50 mass %,

The fusing point of the wax A is 60.0 DEG C to 100.0 DEG C,

The wax A is that the esterification of two with 2 to the 6 carbon atoms pure and mild aliphatic monocarboxylic acids with 16 to 22 carbon atoms is closed Object,

The solubility parameter of the wax A is at least 8.81 (cal/cm³)^1/2,

In the differential scanning calorimetry measurement of the toner,